ITEM No. 8,22 FILE No. XXIV - 19 ANORGANA G.M.B.H. WERK GENDORF COMBINED INTELLIGENCE OBJECTIVES SUB-COMMITTEE ANORGANA GmbH WEEK GENDORF GENDORF. GERMANY MISCELLANEOUS CHEMICALS 1S-19 May 19^5 Reported by: V.C. BIDLACK - TIIC Chemicals F. J. CURTIS - CW3, Hq ETOUSA J. M. HARRIS - CWS, Hq ETOUSA 12 June 19^5 CIOS Target Numbers S/S6, 22/1 (f), 22/534 Chemical Warfare COMBINED INTELLIGENCE OBJECTIVES SUB-COMMITTEE 0-2 Division, 3HAEF (Rear) APO 4-13 TABLE OP CONTENTS Subject Page No* i c General 3 2. Chemicals Manufactured from Acetylene 9 3. Chemicals Projected from Acetylene 19 4* Application Data on Surface Coatings 27 5. Pharmaceuticals —- 28 6. Miscellaneous Items 31 7 • Charts - Acetylene + Formaldehyde —~ 33 -Butyrolactont —————————— 35 Acetylene + Acetaldehyde 37 PERSONNEL OP INSPECTION TEAM Lt. Col. P.R. TIER- CWS,Hq ETOUSA Col.J. H. ROONEY M. of S. Lt. Col. S.B. GORMAGK— M. of S. Lt. Col. J.W. CRAWFORD- M. of S. Major T. LOVE M. of S. Major H.N. RYDON M. of S. Mr. V. G. BIDLAGK CWS,Hq ETOUSA Mr. P. J. CURTIS CWS,HQ ETOUSA Mr. J. M. HARRIS CWS,Hq ETOUSA Mr. I. H. JOKES Petroleum Attache Mr. Gr. M. KLINE OD, Hq ETOUSA Mr. E. B. PECK — Petroleum Attache 2 •S6Ti*.-S ANORGAKA GmbH WERK GENDORF MISCELLANEOUS CHEMICALS 1 • GENERAL Anorgana GmbH was started as a subsidiary of I.G. Farben- industrie AG in June, 1940 and financed by Montan Industrie Werke AG, a subsidiary formed by the German Government to handle such matters. The cost of construction was 120,000,000 marks. During the war and while construction was going on 4000 workers were em- ployed, partly foreign. It is estimated that normally 2000 workers would be needed for full operation and for the present situation about 1000 could be used. a. Organization Names and positions of officials of the Anorgana GmbH: Managing director Dir. Dr. M. Wittwer Inorganic department Dr. M. Gruber Organic department Dr. G-. Hagen Sales Service department Dr. J. E. v. Klenck Accounting W* Jansen Social department Dr. E. Lederle Ordnance department Supt. K. Wurzler Name and position of official of I.G. Farbenindustrie AGt Research and pharmaceuticals Dir .Dr. W. Reppe b. Present Daily Manufacture Leonil (detergent) - 300 kg Luphen (lacquer) - 1,000 kg Ether (narcotic) - 250 kg Ethylchloride techn. - 3>000 kg Etiylchloride pro narpose- 250 kg c. Rav; Materials and Finished Products on Hand Common salt 2.477 tons Formaldehyde 30°/o 30 tons Barium carbonate 354 " Ethylene oxide 52 " 36Ti4,-5 Soda 65*4 tons Sodium bisulphite as S02 100$ 19 " Hydrochloric acid as HG1 100$ 36 ” Graphite 290 " Mercury 62 *7 H Sulphuric acid as SO, 127 " Chlorine 90 w Caustic soda in solution as 100$ 350 w Ferrous sulphate 32.5 ” Nitric acid 62$ 8.4 ” Methylated spirit 270.4 " Phenylglycine 43*6 M Coke 80 " Diethylbsnzene 122 n Sulphur 950 w Chloride of lime 27 n Caustic potash 10 w Calcium chloride 10 w Methanol 0*3 w Ethylene chloride crude 171 n Ethylene chloride pure 208 w Glycol 565 * Diglycol 677 ” Aluminum chloride 6l tons Copper sulphate 2.5 ” Adipic acid 30 11 Ethylglycol 11 " Cere sin 2.5 ” Urea techn. 5 H Resin 6.7 Naphthlene 2 " Ootadeoylaloohol 2.5 ” Castor oil 9*3 * Sesame oil 20 ” Rape-seed oil 4*5 rt Olive oil Illrd quality 4.5 " Paraffin 20 " Stearic acid 11.6 H Benzene 48 " Active carbon 5 ” Orthodichloro- benzene 15 ” Carbon tetra- chloride 2.5 ** Phosphorus- trichloride 2.3 n Triglycol 114.8 w Glysantin with tri (Prestone) 65*7 " Carbide 3*108 Acetaldehyde 380 " d. Supplies Needed Coal Prom; Pensherg or Hausham Coke Munich or other municipal cokeries Carbide Hart Salt Heilbronn near Stuttgart Oils Stores in Passau, TBging and Regensburg Toluene Benzene Phenol Ruhr Territory Ammonia Nitric acid Middle Germany 3&rsuf.-Jt Sulphuric acid Kelheim near Regensburg Nitrocellulose Aschau Peroxide of hydrogen Krai barg Solvents Burghausen Plastics Burghausen Urea Oppau Porraamide Oppau Methanol Regensburg e, Production Capacities in tons/month (1) Lacquers Luphene 35 Phtalop&l 100 (2) Plasticizers Palatinol 50 S or online 10 (3) Plastic* Lupolene 5 Luvitherrae 10 (4) Solvents Glycol 1,000 Glycolether (Ethyl, butyl) 100 (5) Detergents Leonil 50 Igepon 125 (6) Waterproofing Agents Ramasite 20 (7) Organic Chemicals Ethylchloride techn. 90 Etl^ylenechloride ifOO Acetaldehyde 2,000 StTH.*. -JB (8) Inorganic Chemicals Chlorine 2,500 Caustic soda 3>000 (9) -Pharmaceuticals Principal products in kg per month: Ether 5>000 Ethylchioride 7,500 Hartosol 5>000 Postonal 1,000 Specialities in g per month: Kresival 20,000 2ephirol 5,000 Phanodorm 1,000 Evipan 1,000 Eunarcon 500 Novocain 1,000 Adrenalin 1,000 Acetylphenothiazine 500 Avertin 1,000 Insulin according to delivery of glands Periston according to delivery (Solution of butandiol-l,A. f• Research (l) Organic Section Formation of Butadiene out of Ethanol Glycol-ethers V inyl -chi or ide Alcohols of Acetaldehyde Dulcin Textile auxiliaries Ethylbenzene Styrene Polystyrene Lacquers (Resins) Ethylchloride Chlorination of benzene Chlorination of fatty acids 3VT!M<.-3 Polyethylene Oxidation-experiments (ethylbenzene and others) Rubber-ooraposit ions Chloral Insecticides (chloral and chlorobenzene) Purification of crude ethylenechloride Aldol Ether for narcose Grot onalde hyde Crotonioacid (2) Sales management Preparation of varnishes and lacquers based upon Nitrocellulose Phenolic-resins Polyviiy lohl or ides Plasticizers Solvents Resins Shoe-polish Floor-polish Glues Esters of diglycolicacid as plasticizers Polymerization of crude butylene Textile auxiliaries as: Detergents Waterproofing-agents Softeners (3) Inorganic Section Water electrolysis Carbonmonox ide Production of charcoal Regeneration of potassium permanganate Silver catalyst for formaldehyde synthesis Basic Aluminium chloride Phosgene (for organic synthesis) Thionyl chloride (for organic synthesis) Chlorosulfonic acid Ammonium nitrate Aluminium acetate 3 AT**.-* (4) Main Laboratory (a) Pliarmaceutical products: Ether pro narcosi Ethylchloride pro narcosi Mitigal (DimethyIthianthrene) Hartosol (isopropylalcohol) Kresival (Calcium salts of eresolsulfonic-acid) Zephir ol (D imetliyl - be nzyl-aliyl -ammonium - chloride) Phanodorm (5-ethyl-A-1-cyclohexenyIbarbituric- acid) Evipan (3#5-Diinethyl-5-A-l-cyclohexenyl- barbituric-acid) Eunarcon ( 3-Me thy 1-3-H -bromallyl-5-isopropyl- barbituric-acid) Novocain Adrenalin AcetyIphenot hiazine Avertin (i.1.1-Tribromoethanol-2) Insulin Postonal Abasin ( 1-Acetyl-3-(bromodiethyl)-acetyl- carbamide) Perist on (poly-N-vinylpyrrolidone ) Sulfonamide: Frontosilum album Pyrimal Eleudron Eubasin Urotropine (Ilexametbylentet ramine) Camphor oil Barium sulphate (b) Organic Intermediates: Formaldehyde from methanol Ethanol from Ethylene Octadecylalcohol from vegetable oils by high pressure hydrogenation Higher alcohols from long chained olefines Ester of Oxyraethylviry Ike tone from butin-2- diol-1,4 5b72.fc.-3 (o) Plasticizers, lacquers and plastics section: Resins of phenol formaldehyde (Luphen L) with or without plasticizers Resins of phenol acetylene for plastics Resins of melamine formaldehyde by reaction of dicyandiamide with melamine (nitrogen calcium) Organic t hi oplastics (Thiokol a*s*o*) Ethyl cellulose (d) Textile auxiliaries s Igepon A with intermediate products Igepon T from E thy lamina including inter- mediates* Igepon from monoethanolamine (e) Inorganic auxiliaries s and SCI 2 2 2 Interviewed: Dr* Ambros* 2. CHEMICALS MANUFACTURED FROM ACETYLS NS a* Preparation of Acetylene Acetylene was made at Gendorf from calcium carbide produced locally (Trostberg)* In spite of the high cost of the carbide (180 RM per T) it is claimed that ethylene (See b below) made from acetylene was cheaper than ethylene made from ethanol* Acetylene was generated by both the "wet” and the "dry" gasification processes* The "wet” process, in which carbide was fed to water in an agitated vessel and the resulting lime slurry thrown away, is old and needs no farther description* The gener- ator used for the "dry” process consisted of a rotating cylinder containing an inner wire mesh cylinder about 8 inches smaller in djameter* The two cy7i.inders rotated about an axis inclined about 8 from the horizontal after the manner of a rotary kiln drier. Carbide was fed in lumps about the size of a walnut to the upper end of the generator and was tumbled about on the rotating screen* Water was added at five different points causing the evolution of acetylene and the lumps of carbide to crumble to a dust which passed through the wire mesh inner cylinder and rode to the lower discharge end of the generator through the annulus between Sb7X.tt.~S •9 the two cylinders* The Ca(0H)2 discharged contained about 5% water and could be readily handled by a screw conveyor* The acetylene was dried by passage over the incoming carbide, passed through cyclone dust separators and finally emerged with a purity of 98%, The chief impurity was nitrogen with which the carbide was blanketed during shipment. According to Dr. G-ruber, the operation of the *dryw generator had been unsatisfactory and several difficulties (e.g. the steady feeding of the carbide) had not been eliminated. Acetylene from carbide was pure enough for the preparation of acetaldehyde, but before it could be hydrogenated to ethylene it must be purified as follows: I - Scrubbed with dilate chlorine water to remove HgS and PH,. II - Scrubbed with a solution of caustic soda to remove chlorine and for partial drying. An attempt was made to purify the acetylene by passing it through active carbon but the process was unsuccessful and was abandoned. Carbide was used in the amount of 150,000 tons per year - equivalent to about 47,000 tons of acetylene • b. Preparation of Ethylene from Acetylene Ethylene was prepared by the hydrogenation of acetylene. The acetylene was prepared and purified as described above. The hydrogen was a mixture of electrolytic hydrogen and hydrogen pre- pared by the ”steamiron" process. It required no purification as its chief impurity was carbon monoxide, which was hydrogenated to methane and did no harm. The reaction was carried out in 22 converters arranged down two sides of a large building, 20 of these manifolded so that they may be operated in parallel. All the production of these 20 was passed through the other two in series for the removal of the last traces of acetylene. The converters were vertical cylinders about 10 ft. in diameter by 15 ft. high. Inside each cylinder were alternate layers of catalyst and bubble cap plates. The plates act as gas distributors and did not support any liquid. The gas mixture recycled through the con- verters contained about 5$ acetylene, 8$ hydrogen, water vapor and ethylene. The converters were operated at 7-10 p.s.i.ga. and at a temperature of 180-320°C depending on the age and adtivity of the catalyst. 3<»ys.tt. - 3 Fiqu re X EthqleneChlorhqdnn Equipment G e n d o r f Wote r ft ecuole c2 h4 c i (oh) HC I C, HiCU Water. 1/ent C h 1 o r i n & Chlorine Water 10“ 15°C 1 &Q po h i f i c t* * n gi e n e (T) Feactor i BricUlihed C.I. x 12M (2) Condenser - Scrubbe r; B rick 1 med C.I. 0 Still Uq-for deqasificaiion of product ® blower ~ to recqde qoses (5) Pipe conv'eqinq liquid - qas mixture to still Leq. 0 Pipe returnincj qases to reactor Mavj 2®, The catalyst was silica gel containing traces of palladiums the exact amount of palladium not being known as the catalyst was prepared at Ludwigshafen• It was estimated at 4-8 parts per million. Catalyst .life was about 12 months. The exit gas after cooling contained 65$ ethylene and was free from acetylene. It was dried over silica gel and liquefied by the Linde Process. A three column system was used. The partially liquefied mixture was fed to the middle of the first column from the bottom of which high boiling compounds (C, -Gq) are removed. Hydrogen, methane and nitrogen were removed from the top of the second column from the bottom of which liquids passed to the side of the third column. Ethylene passed from the top of the third column and ethane from the bottom. A second fractionation of the ethylene will give material free from ethane and having a purity of 98$ but at an appreciable extra cost. The output of the G-endorf plant was 25*000 to 30,000 T. ethylene per year. c. Preparation of Ethylene Chlorhydrin Ethylene chlorhydrin was prepared by the action of chlorine and water on ethylene. The equipment is sketched in Figure I. Ethylene was fed to the side of the reactor and chlorine at points above and below the ethylene. The following reactions occurred: (ethylene chlorhydrin) There was also a side reaction: (dichiore thane) Four of the units described (Figure I) required per hour: 2000 V? Ethylene (gas) 1000 V? Water (liq.) 6000 kg Chlorine The Ghlorhydrin produced was not isolated but was hydrolyzed immediately to ethylene oxide. The yields of chlorhydrin were not known but the above feed rate produced 2.7 T. of ethylene oxide per hour. Diehlorethane in the amount of 0.7 T. per hour was produced simultaneously. 3&T2.^.-3 F i q u r e It Ethqlene Oxide Equipment CZH4O H20 60& HzO 56%' Ca(0A]2\2% c2h4(oh)ci. -IOO°C Plates heated tndirecflq with Steam ~ 0 Soponifier C.I. 2.5M(J)X 6M 0 Oephieqmoiior to reduce loss of wafer with product /jn Plates, steam heated, with., vertical baffles to qive lanq tortuous path for reaction fnixt. J.WA.H. Moq 5Q FM5- 367Z/J.-3 Gendorf operating personnel believed that future chlor- hydrin reactors should be made smaller and that all the chlorine should be introduced below the ethylene inlet to suppress the formation of dichlorethane• The latter modification is based on the theory that if all the chlorine has reacted with the water before ethylene is introduced, reactions I and II occur* If chlorine comes in direct contact with ethylene reaction III takes place• d. Preparation of Ethylene Oxide Ethylene oxide was prepared from the chi or hydrin by the following reactions The reaction was carried out in the equipment sketched in Figure II* There are four of these "saponifiers*1, each connected directly to one of the four chlorlydrin units described in Figure T# The chlorhydrin, HG1, water mixture and milk of lime were fed to the saponifier through concentric feed pipes in the proportion of 2 vol. chlorhydrin mixture to 1 vol* 12$ Ca(0H)2 slurry* The resulting reaction slurry was led through a long tortuous path in the saponifier on baffled, steam heated plates as shown* Ethylene oxide and steam distilled out the top of the reactor through the dephl- egmator which removed some of the steam. A calcium chloride - calcium hydroxide solution was dhawn off from the bottom. The ethylene oxide-water mixture was fractionated in a three column, continuous distillation unit. The first two columns operated in parallel and received the ethylene oxide - water mixture from the "saponifier." They contain 50 bubble cap plates and received theQfeed on the 17th plate* The reboilers were steam heated to 55 0* The top column temperature was 12°C. These two columns were operated with a reflux ratio of 3/1 and produced Aj0-50 T. per day of 98$ ethylene oxide. Residues from the first two columns were fed to a third column having a reboiler at 80°C. The water was removed from this reboiler. Vapors from the third column were fed to the first two columns on the 33**8. plate • The yield of ethylene oxide based on ethylene amounted to 70 - 75$ of the theoretical. All three columns were made of oast iron. S67ZM.- I Dichlorethane was removed from the hot tan of the third column, washed with sulfurio acid, hydrochloric acid, and caustic soda solution and finally distilled batctarise* e • Preparation of Glycols Ethylene glycol was prepared by the reaction* Steam and ethylene oxide were passed up through an iron column packed with steel Raschig rings* The ethylene glycol pro- duced was purified by fractionation* By altering the temperature, pressure, and feed ratios the same equipment can to used for the production of diglycols, for examples f. Detergents "Leonil" detergents were made from long chain alcohols and ethylene oxide* The type reaction is; The compound made from 8 ethylene oxide molecules and one aloohol molecule is water soluble and is a detergent* The com- pound made from stearyl alcohol was made up as a 30$ water solution and sold as "Leonil 0 Lag," or Genapol* It was actually being sold in considerable quantities because of the soap shortage* As it contains no sodium it cannot form salts and may, therefore, be used with hard or soft water* It is excellent for wool scour- ing in either acid or neutral media* When used for domestic laundry soda is added* It does not foam and therefore does not sell readily* As of May 19, 1945» enough raw material was available at Gendorf to prepare 42 T of Genapol (weight of water included)* For subsequent production it will be necessary to prepare the fatty alcohols by hydrogenation of fatty acids* These compounds were prepared in an enamel lined kettle under 45 p*s*i*ga* and at 165°C* The fatty acid was charged and the ethylene oxide introduced until the batch shows the correct titre, sp.gr., mol. wt., etc. The preparation of "Igepon 0" may he outlined as follows: "Igepon A” "Igepon A” decomposes at about 100°G; therefore it cannot be used if laundry must be boiled* "Igepon G-" was not made from ethylene oxide. Its preparation is outlined in section 6 of this report (miscellaneous chemicals). g. Emulsifiers Compounds made from 20 ethylene oxide molecules and one' fatty alcohol molecule sure emulsifiers sold as "Eraulphor Cw ani were used in the preparation of emulsions used for spinning wool. One oleic acid molecule combined with 6 ethylene oxide molecules gives Emulphor A, used for emulsifying machine oils like spindle oil. Castor oil plus 40 ethylene oxide molecules gave "Smulphor E.L." h. Textile Aids Compounds of 20 ethylene oxide molecules with one fatty alcohol molecule, were used as levelling agents for dyestuffs and were sold as "Polatinechtsolze." A water solution of this material was sold as "Diazopon"; a solution as "Peregal 0." Stearic acid combined with ethylene oxide gave "Soromin S.G.", which was sold as a softener for artificial silk. i. Waxes Waxes may be made by the polymerization of ethylene oxide - the so-called "polyethylene oxide waxes.” None have been prepared at Gendorf lately. E.L." J4TM.-S Condenser. C- I- Jtr.A.H. Moq5l, ISA5 Water Acei ic Acid water ocrubber (?) Dilute Aldchtjde Storoqe (S) Tract. Col. - 2S Plote6 finished Prod. 51 o r a q e Fiqur e HI Ac eta Ids hqde Equipment Water (T) Reaction Tower © Condenser © Mercury Separator steo m Acet ij lene S5°C Cot ' HS._ aj»7s.*.-3 3* Thiodiglycol (Oxol The thiodiglycol plant had never been run and Dr. Hagen was unable to give ary data as to production capacity. An aluminum tower, 6 m high x 0.66 m dia., packed with Raschig rings and equipped with cooling and heating coils is filled with thiodiglycol from previous manufacture. Hydrogen sulfide gas and ethylene oxide are passed in at the bottom maintaining a temperature of 90°G. The product overflows continuously to a cooler and to storage. Com- plete absorption of the gases is obtained. If it is desired to purify the thiodiglycol, it is dried under vacuum and treated with enough ethylene oxide to unite with the hydrogen sulfide present as determined by titration. k. Acetaldehyde from Acetylene Acetaldehyde was made from acetylene in two units and the crude product was purified in a continuous fractionating column. Production from the two units amounted to 1800 T. aldehyde per month. The essential reaction is; This reaction was carried out in two vertical cylinders about 2 m. diameter by 8 m. high. These cylinders are made of V2A and contain no packing. The heads are designed to act as entrain- ment separators. A layer of mercury stays in the bottom of the reactor at all times. The reactor was charged with a batch consisting of; 3000 kg Pe SO, 1600 kg 8400 kg Y/ater Acetylene in the amount of 860 per hour and under a pressure of about 25 p.s.i.ga. was introduced below the level of the mercury which is thereby agitated until there was a mercury emulsion throughout the batch. Live steam was introduced near the bottom to help the agitation and to keep the batch temperature at about 95°C. Approximately IT. of steam v/as required per batch. The vapors from the top of the reactor were cooled to 40°G by passage through a water cooled condenser* They kthen passed to a mercury separator from which mercury and condensate passed back to 3 6T»*.-3 the reactor tower. Mercury lost by this process amounted to 1 kg per T of aldehyde produced. Vapors from the mercury separator passed to a water scrubber packed with Raschig rings in which the aldehyde and a trace of acetic acid were washed from the gas. The scrubbing liquor from the bottom contained about 7*5% aldehyde plus a trace of acetic acid. It was sent to a continuous fractionating column. Gases from the top of the scrubber, chiefly acetylene, were x-ecycled to the reactor. The aldehyde solution corresponding to an acetylene feed rate of 860 per hour amounted to 21770 kg per hour. It passed through a heat exchanger, a steam heater, and was fed to the 21st plate of a 29 plate column. This column is 2 m in diameter by 10 m high, from the feed plate down, it is const meted of V2A, Above the feed plate it is cast iron. The top column temperature was 21 C, the boiling point of pure acetaldehyde. The roboiler temperature was 100 C, The residue from it was water plus a trace of acetic acid. The reflux ratio was constant at 2/1. The aldehyde taken off was degassed in a small column with a reboiler at the bottom. The acetylene recovered was put back in the recycle gas. The final pro- duct from the reboiler was 99*9% acetaldehyde. During the reaction the ferric iron content of the catalyst solution gradually decreased until a point is reached at which con- version fell off. The catalyst was then drawn off to a settling tank in which the mercury settled out. It then passed down through a brick lined tower packed with ceramic Raschig rings in which it was blown with live steam. Next it went to a second settling tank in which more mercury was recovered, and from there to the oxidizer. In the oxidizer the ferrous iron v/as oxidized continuously to ferric with nitric acid." On leaving the oxidizer, the solution was dark brown due to the presence of which was broken down by air blowing. The oxides of nitrogen from the blowing were recovered by water scrubbing in 5 towers in which the water was recycled counter current to the gas flow. The 15% nitric acid thus obtained v/as blended with fresh acid to a concentration of 25% and used again in the oxidizer. The catalyst solution after air blowing was ready for reuse* 5. CHEMICALS PROJECTED FROM ACETYLENE Dr. Reppe removed his laboratory to Gendorf when it v/as bombed out at Ludwigshafen last fall. Dr. Reppe is a very creative re- search worker on the reactions of acetylene and has evolved a large number of schemes, few of which have been put into operation. S672*.-3 a• General Schemes for Development of Acetylene Compounds Much of the framework of Dr, Reppe*s ideas is contained in the three attached charts; (1) Acetylene + Formaldehyde. (a) Y- butyrolactone. (2) Acetylene + Acetaldehyde, b. Processes Reduced to Practice (1) 1*4. butanediol (1,4 butylene glycol) Several thousand tons/mo, of 1,4 butanediol were pro- duced at Ludwigshafen, largely as an intermediate for butadiene. 1,4 butinediol was first made in a tower 18 m. high x 1.5 m. diameter containing 20 cu. m. of a contact mass of copper acetylide on silica gel where the copper compound is 10-12$ of the contact mass. Five times the theoretical acetylene and formaldehyde diluted to 10% with liquor from the bottom of the tower were passed into the top of the tower under a pressure of 5 atmospheres of which 4 were due to acetylene and 1 to water vapor evaporated in the process. Temper- ature was 100 Go 1 cu. ra, contact mass produced 1 ton of 100% butinediol per day. The product was a 30$ solution in water, which can be evaporated off and the diol crystallized from ethyl acetate. The diol can be distilled under ordinary pressure. Propargyl alcohol goes off in the first part of the distillation and can be recir- culated with the formaldehyde. The reaction is; A side reaction to give propargyl alcohol also takes place; Yields are; Acetylene 92$ Formaldehyde 95$ + 4$ to propargyl alcohol The 1,4 hutinediol was hydrogenated by running it down a tower over copper nickel in the presence of hydrogen at 200- 300 atmospheres and at 80-130 • A yield of 96$ to 1,4 butanediol S6TZ4--3 20 was obtained with the balance going to butanol# Coat of 1,4 butanediol were 60 pfg/kg and it is expected that it may be reduced to 40# o. Tetrahydrofurane and Adipic Acid Tetrahydrofurane was produced from 1,4 butanediol in 92$ yield by passing over a catalyst of phosphoric acid containing 3/2 - 1$ phosphine at 260°C and 70 atmospheres pressure# The product is a good solvent and is known as Losungsmittel T# When tetrahydrofurane was reacted with two mols#, carbon monoxide and one mol# water at 200 atm# and 270°C with 10$ nickel carbonyl a yield of 90$ of adipic acid was obtained# In practice the water containing 1$ of its weight of iodine in the form of niokel iodide and the tetralydrofurane in which the niokel carbonyl is dissolved were passed into the bottom of a tcwer with the CO gas. Adipic acid flowed out the top pre- sumably with sane tetrahydrofurane. The GO gas and nickel car- bonyl passed to a separator to remove the latter and the CO re- turned to the tower. Throughput of the tower was 300-600 cu. n/hr. of the furane. d. Propargyl Alcohol The reaction for 1,4 butinediol can be run to give 80$ propargyl alcohol instead of 4$ if desired. By hydrogenation with an iron catalyst under pressure, propargyl alcohol was converted to allyl alcohol and with a copper catalyst to propionaldehyde• Oxidation of propargyl alcohol with air at 50°G over a cupric chloride catalyst gave hexadiindiol 1,6 HOHgC - G: a C - C a C - GHgOH which on further reduction goes to the hexanediol 1,6. By conversion of the hexanediol to the double aldehyde followed by an internal Canizzaro reaction g-caprolactone GB^GHgCHgCHg I ! CH2 -0 - OG is formed which is converted with ammonia to the £ -caprolactam OT GHg-MT- OC for the polyamide known as Igamid B. e. -y-Butyrolactone and N-viryl Fyrollidone 1,4 butane diol may be dehydrogenated in a tower in the presence of copper strips at 200°C to form y butyrolactone in 96$ yield* Reaction with ammonia gives a 90$ yield of pyrollidone which on treatment with acetylene furnished N-vinyl pyrollidone in 90$ yield* — CHo \2 CHo G = 0 V ✓ N f CH = CEp The N-vinyl pyrollidones are the bases of a new series of polymers, largely water soluble and of a character resembling albumen* They are used for glues and plastics but few uses have as yet been developed except the blood substitute ’’periston”, de- scribed in report on the I.G. at Elberfeld* The degree of poly- merization is controlled by the amount of hydrogen peroxide which is varied from 0.05 to 1.0$. The more peroxide used, the shorter is the polymer chain. (1) Methods of polymerization (a) Bloc]:, type 35 kg K-vinyl pyrollidone were mixed with 150 cc 3C$ peroxide solution and UK, equivalent to 3/2 the ILOg and heat- ed to 110°C. Without further heating the temperature went to 180- 190 C. The hot polymer flowed out of the kettle and was cooled in blocks. The product has a yellowish color due to the high temperature, has a low K value (30-35) and contained about ICf/o monomer which was extracted with ether before solution of the final product in water and filtration. ,rPeristonu is a 2.5?o solution of a product made in this way where the temperature is kept to 70-80 G. These products can be used as glues and binders for films, for adhesives, thickeners for emulsions and solutions, and assistants in dyeing causing darkening of the color. 3672.* -» (b) Solution Type To 30 parts N-vinyl pyrollidone in 70 parts water was added 0.5 parts 30$ peroxide solution and 0.1$ ammonia (100$) at 20°C. In presence of the oxygen of the air no reaction takes place, but in a stream of nitrogen it begins immediately and is complete in 2 hours. The product has a K value of 56. (2) Acetylene polymers Cyclopolyolefines By condensation of an excess of acetylene under a total pressure of 10-20 atmospheres of which 5 atmospheres is nitrogen partial pressure and in the presence of a solvent such as tetra- lydrofurane, cyclooctotetraene CgHg was obtained at 60-70°C in liquid phase by means of a catalyst of nickel cyanide on a carrier with a yield of 90$. The reaction took place in a tower, both gas and liquid entering at the top. The liquid product v/as distilled and the tetrahydrofurane returned for reuse. Small amounts of C1qH-Lq and soluble resins, and cuprene were also formed and particularity dy raising the temper- ature the proportion of these can be increased. The best temperature for is 80-90°C and for about 130-140°C. Azulen forms as a by product when the temperature is 80-130°C. Gy cl 00c t at etraene CgHg 142-143°C Golden Yellow Cyclodecapentaene G SPg 48-50°b BP?50 190-195°C Deep Yellow Cyclododeoahexaene G BPn c, 60-65°Q 230-235 G Bright Yellow Azulen C10H8 W 99.5°C Deep Blue The constitutions of CgHg and of Azulen are definit- ely determined, the former being: OH » GHV GH GH 5h > = GH The constitutions of CinHnQ and need further clarification. The CqH8 and have been investigated pharma- cologically v;ithout finding ary action. On the contrary. Prof. Kuhn 36Ti*.-5 determined that the growth of certain pathogenic bacteria was completely suppressed in a dilution of 1:100,000 by the fraction which because of small amounts of azulen (about 5%) was colored deep blue. (3) Ethyl Alcohol Dr. Reppe claimed that a practical process bad been developed for direct hydration of ethylene which, in Germany, is likely to be produced from acetylene. The process is applicable also to propylene and butylene. The olefine and water were run into the top of a tower packed with a catalyst consisting of a mixture of WOg and WO, made from ammonium wolframite and promoted with 5$ zinc oxide. The catalyst is carried on silica gel and the mass contains 20$ W. in the tower was 200-300 atmospheres and the temperature 300 0. In practice the whole system was kept under ethylene pressure as above, new ethylene being pumped in to replace that used up. A 20$ solution of ethyl alcohol flowed from the bottom of the tower to the rectifiers. The catalyst converted 1 liter ethanol per liter catalyst per hour. (4) Acetylene and Alcohols The type reaction for aliphatic alcohols is; RQH + C2 = ROGH: dig This reaction must be carried out with the alcohol in the liquid phase. The lower the molecular weight of the alcohol, the lower the optimum temperature of reaction, hence when the boil- ing point of the alcohol is lower than the reaction temperature, sufficient pressure must be maintained to keep the alcohol in the liquid phase. (a) Acetaldehyde These principles are used in the Reppe process foi* acetaldehyde which is not new. Methanol is treated with acetylene at 20 atmospheres pressure and 90 C to form methyl viryl ether. By treatment of the latter with water vapor at atmospheric pressure, iydrolysis takes place to methanol and vinyl alcohol, the latter immediately rearranging to acetaldehyde. The methanol is reused. Since the process uses no mercury, which became scarce in Germany, a plant for 200 tons/raonth was erected in Ludwigshafen, but was bombed out after being operated for a short 36T*-*.- 5 while* Mercury poisoning troubles are eliminated, but Dr* Reppe admitted that the method was somewhat more expensive than the con- ventional mercury process* (b) Polyvinyl oleyl Ether The reaction of acetylene with oleyl alcohol takes place at 130-180°C with the use of 1% KDH as catalyst. No pressure is necessary* A 4 cu. m* tower capacity produced 10-20 tons/day at yield* The polymerized vinyl oleyl ether is used as a pour point depressant for lubricating oils, but Dr* Reppe could furnish no details of its effectiveness. (5) Vinyl Phenols In the aromatic series' phenols and naphthola react as follows; Phenol was treated with acetylene in the presence of zinc naphthenate catalyst at 10 - 20 atmospheres and about at its boiling point (182°C)* The vinyl phenol polymerizes directly* By reaction of these compounds with hexamethylenetetramine a * series of resins were produced with properties varying from thermo plastic to thermosetting depending on whether 1, 2 or 3 molecules of acetylene are reacted with the phenol* Koresin for synthetic rubber was made similarly, starting with butyl phenol* (6) Acrylic Acid Acetylene in its isofom H C = cC. reacts with CO to give methylene ketene H|C=C=CO which in turn gives HgCssCH GOOH, acrylic acid* In practice the reaction runs; H2O + + 1A Hi(OO) + yz HC1 Aq = HgC = OH COOH + 0/4 Aq + 0/4 Hg. Alcohols can be substituted for water to give the ester* Stoichiometric proportions of raw materials are used with the nickel carbonyl furnishing the (X); the presence of acid or halogen is necessary to bind the metal of the carbonyl as a salt* Technically hydrochloric acid was used and the reaction ran 5i 7,SJf. -3 very actively at 40-42°C with practically quantitative yields of acrylic derivatives. In the laboratory process for the preparation of ester, alcohol is placed in a three-necked flask with the cone HC1, the air is swept out with acetylene and the necessary amount of nickel carbonyl allowed to drop out of a burette. Temperature is 40-42°C• It is important that sufficient acetylene be furnished, as otherwise the rate of absorption is so great as to form a vacuum. After distillation of the acrylic ester - alcohol mixture from the nickel chloride, the acrylic ester is obtained in pure form-by washing and distillation. Regeneration of the nickel carbonyl from nickel chloride is carried out ty treating the chloride solution with a slight excess of ammonia above that necessary to form the complex hexamin nickel-2-chloride and then with CO at about 80 °G and 50- 100 atm. The nickel carbonyl is formed quantitatively, leaving in solution the excess ammonia, ammonium chloride and ammonium car- bonate • The acrylic acid process can be run continuously and without pressure except in the recovery of nickel. (7) Products from Butadiene As butadiene in Germany is produced fundamentally from acetylene. Dr. Reppe*s ideas on this subject are included herein. Butadiene in benzene as a solvent is converted to vinyl oyclohexene at 270°C and 200 atmospheres with nickel carbonyl as a catalyst if no water is present. 70 - 90% yield is obtained. In the presence of water four products are obtained: COOH CHCHj COOH v O' CHaCH 0-oh^ With longer time a mixture of the following which cannot be separated is obtained; COOH H00C 'rOl “^hch3 0 COOH /■vCHGH} 0 hdcxT^-^ COOH GOOH WOC 5672-/f-3 The mixture serves as a base for plasticizers and when free of monocarboxylic acids, for polyamides* 4. APPLICATION DATA ON SURFACE COATINGS Lacquers, varnishes, waxes and emulsions were discussed; none of these products were being made at Gendorf but were made by I.G* Parbenindustrie in Ludwigshafen. Essentially, they produced the basic materials for further processing by surface coating manu- facturers • Lacquer information possessed at the Gendorf plant is based on standard formulation using glycolesters as the active solvents for nitro cellulose, cellulose acetate, cellulose butyrate and cellulose trix>ropionate, The resin portion at this time is ester gum, although various synthetic resins will be employed when avail- able. The diluent is benzene which is apparently permissible in Germany regardless of its toxicity. Synthetic waxes were purchased from Ludwigshafen and the harder types were preferred in the 12G to 18G series,'such as the palmitic esters. Consideration is being given to the manufacture of resin emulsions and these will be based on modifications of methacrylate, polyvirylacetate and phthalic anhydride resins. Production of these products will depend upon the availability of the necessary raw materials at Gendorf. Three grades of so-called varnishes, sold under the trade name Luphen, v/ere made in Ludwigshafen. These are condensates of the phenol-formaldehyde type in butyl alcohol. The end product contains 75% resin and 25% butyl alcohol and is known as Luphen L. The process involves the reaction of approximately 1 part phenol, 1 part aldehyde in the presence of 4 to 6 parts butyl alcohol for 6 to 8 hours at 120 to 140°C. The addition of 1 to 5% HG1 just prior to application is employed for final conversion of Luphen L resin. Ordinarily the resin solution was reduced to 50% solids with alcohol for spray purposes and was used where chemical resistance is required. Lupen 0 H is Luphen L without hardener and is recommended for finishing wood or metal, either clear or pigmented. The reaction for Luphen 145 is not carried as far as Luphen L and is soluble in ethyl alcohol. It was primarily used for can coatings which are baked at l65°G. 3471*.-S Chlorinated polyvinylchloride resin under the trade name Vinoplex was made at the Bitterfeld plant of I.G-, Parbenindustrie. It was produced by passing chlorine gas into a 20$ solution of polyviryl- chloride resin (32 to 3&% Cl) in carbon tetrachloride at 30 to 40°C* resulting in the addition of 2 to 4$ chlorine above the theoretical amount. The dried product (Vinoplex) is a white powder which is soluble in mixed solvents of ketones and aromatics and the cast films have excellent chemical resistance. ’This is the basis of IGELIT-PC. Other products which are on the agenda of the laboratory for further study are the chlorinated Buna rubbers, chlorinated polystyrenes and polyethylene resins. The interview was with Mr. Eichstadt, Ghem. Engineer. 3. PItAPMAGSUT ICA3J3 The work on pharmaceuticals at G-endorf is entirely in the lab atory stage. The following notes were given as indicating the directions of work: a. Phanodorm and Evipan Condensation of cyclohexanone with malonic ester in the presence of piperidine acetate gives cyclohexylidene malonic ester. Gyclohexenyl ethyl (or methyl) malonic ester is obtained by treat- ment ’with sodium ethylate followed by reaction with ethyl bromide or methyl iodide, phanodorm (MP 171 o) is produced by condensation of the ethyl compound with urea and Evipan (MP 346°) by a similar reaction of the methyl compound with methyl urea. b. Avertin (Tribromoethyl Alcohol) Equimolecular amounts of bromal and benzaldehyde are re- acted with good cooling in the presence of about 30% on the weight of bromal of aluminum isopropylate in solution in absolute ether. After completion of the reaction, the batch is heated 1-2 hours on the water bath, the mixture is decomposed with 3% hydrobroraic acid and then taken up in ether. The ethereal solution is washed with pure water, then with dilute sodium carbonate solution and dried over sodium sulfate. After distilling off the ether the remainder is distilled under reduced pressure. Boiling point = 92 - S4°C. For further purification the avertin fraction is re- crystallized from petroleum ether - MP = 80°C. 34T2.4.-B c. Adrenalin The preparation of adrenalin takes place in three steps; (1) Pyrooatechol is dissolved together with monochlor- acetio acid and phosphorus oxychloride in dry benzene and boiled 24 hours under a reflux condenser. Dioxyphenyl chloromethyl ketone is formed and is obtained from the above mixture after volatil- ization of the benzene in vacuum and after heating up with carbon tetrachloride by crystallization from water. M.P = 173°G. (2) The powdered dioxyphenyl chlormethyl ketone in alcohol suspension is shaken with a aqueous solution of methyl amine for 24 hours, then filtered washed with cold alcohol. The 4-methyl amino acetopyrocatechol formed is purified by solution in hydrochloric acid and reprecipitation with ammonia. The decom- position point is 230°C. (3) In the last step the above compound is reduced, either in the presence of aluminum amalgam or eleotrocatalytically by means of a nickel or palladium electrode and addition of a palladium chloride solution, to the optically inactive d,1 adrenalin. The inactive forms can be separated by means of the bitartarates into the optically active components. d. Eunarcon N-methyl-5 isopropyl bromoalkyl barbituric acid.- Molar amounts of isopropyl bromide and sodium malonic ester are reacted. The isopropyl malonic diethyl ester is again con- verted to the sodium compound and decomposed with oC bromalkyl bromide to isopropyl bromalkyl malonic diethyl ester. The pre- paration of the bromalkyl bromide takes place according to the publication of Von Tollens by decomposition of 1, 2, 3 tribrom- propane in ether solution with sodium. By condensation of the isopropyl bromalkyl malonic diethyl ester with methyl urea, ring closure takes place to N-raethyl-5-isopropyl brcmoalkyl barbituric acid. e. Insulin Extraction of the comminuted pancreas glands with dilute 60% alcohol containing HC1 is followed by filtration and pre- cipitation of impurities by ammonia. Sulfuric acid is added and the alcohol distilled off in vacuum at a maximum temperature of 30°C* The insulin is fractionally precipitated from the aqueous solution with salt and finally by repeated precipitation at the isoelectric point. The insulin is crystallized from phosphate buffer solution after addition of zinc chloride. SbTJL/i. - 5 f. Zephirol Dimethyl benzoyl alkyl ammonium chloride, A fatty alcohol such as octadecylalcohol is converted at 130 G in a corrosion-resisting autoclave with dry HC1 gas under pressure to the corresponding alkyl chloride. The chlorohydro- carbon purified by distillation under high vacuum is brought into reaction at 100-130°C with 1,5 mols, dimethylamine in benzene solution. The hydrochloride obtained is crystallized from alcohol, slurried with ether and the free amine prepared by shaking with caustic potash solution. Finally the nitrogen of the dimethylamino octadecane is converted to quaternary by addition of 1 mol, of benzyl chloride. g, Mitigal Dime thylthianthrene • A solution of 600 gms SGI in 1,2 liters toluene is allowed to flow into 2.8 liters of toluene and 400 gms aluminum chloride with heavy stirring. Stirring is continued at room temperature. The reaction product is poured on to ice and separated. The excess toluene is removed thru steam distillation and the reaction mixture given a fractional distillation. Chief product = 170 - 180° • h. Novocaine P-nitro benzoyl chloride is condensed \vith diethylamino ethanol in boiling benzene. The p-nitrobenzoic diethylamino ethyl ester is reduced with a chrome nickel catalyst at 2 atmospheres pressure. The amino compound is converted into the hydrochloride, Novocaine• i • N-Ace tylphenot hiaz ine cw COGH^ A mixture of diphenylamine and sulfur is heated whereby phenothiazine is obtained. OCO 3672. **.-3 This is heated with acetic anhydride, whereby the nitrogen is acetylated. Actually a mixture of sulfur and acetic anhydride can be heated together, and also obtain the N-ace tyIphenothiaz ine• 6, MISCELLANEOUS ITEMS a, Igepon G-. The preparation of Igepon G- may be outlined as follows: H H —* -G -GaO -G -CI^GHsNH Acetaldetyde Aldol Aldimin© h2 H „ > CHj-C-CU2-CHg mQH* 0H (oleio) 3 OH 2 * Amine hso3ci GH,. CH-CIU-CHpMiOGR OSO^Na "Igepon Gf" "Igepon G?" b. Water Softener - "Trilon" The sodium salt of the compound prepared by the reaction ' is a water softener sold as "Trilon," Manufacture was started at Ludwigshafen just before the war. c. Detergent Dr, Reppe spoke of work done on a detergent developed by the Japanese, Dr, Otta, with whan, however, he claimed to have no direct contact. The product is made by reaction of a fatty acid amide and formaldehyde -‘sulfite - This is not as good as the Igepon but is cheaper and easier to manufacture. 3C,73Ut--i cU Ramasite Ramasite is a water proofing agent consisting of an emul- sion of paraffins (from brown coal) of different types hard ani soft with less than 1% Nekal with a solution of basic aluminum acetate (or formate or chloride) and urea* For use the emulsion is diluted 1 to 10 or 20 with water and the fabric drenched, then dried at over 100°0 for the formates but at 70°C for the acetates. The water proofing effect is stated to be better than Yelan (Zelan) but is removed by washing. e. Blattan Dr. Ambros mentioned a contact insecticide developed by Dr. Schroeder at Elberfeld - 0 CK Hfil N - P j f• Polystyrene A styrene polymerisation tower had been shipped from Lud- wigshafen to G-endorf and was lying in the freight yard. It was built of five steam Jacketed sections and contained two steam coils in the lower sections. In practice the monomer styrene would pass to two prepolymerization kettles in parallel where it would be held with stirring at 50 - 80°C for two days catalyst. From these kettles it passed to the top of the tower at 70 C and flowed slowly thru with a total time of sojourn in the tower of 24 hours. The temperature down the tower gradually rose to 200°C at the conical exit which was heated electrically. The tower was estimated to be 15 feet high x 2.5 feet diameter and to produce 1 ton polystyrene per day. Prom the conical outlet the molten polymer passed thru an electrically heated screw conveyor to a continuous metal belt carried on cooled rollers where it solid- ified and passed to the guiding system. The chief grades of polystyrene produced were No. 5 with a molecular weight of 100,000 and No. 4 of 200,000. The No. 3 grade being the most important. It was stated- that the styrene is completely polymerized. 3672. *"5 * * Poly amid resins Allyl alcohol —> glycerin Propionaldehyde -»2 methyl butanol 3 al 1-* 2 methyl butanediol 1,5-) isoprene ' Hexadiine 2.4 diol 1,6—* Hexanedicl 1,6 —4 £ Capro- lactam * £ caprolactam—> polyamides 1,4 dichlorbut ine di- acetylene n-butanol Racemic or meso Eiythritol 1,4 dichlorobutane Esters e.g, maleic & polymers Addition products e*g* to anthracene keto- Tartaric acid 1 Malic acid V 4" Plastics Polyurethanes Succinic acid pimelic acid ACBTYIENB + PQRMAIJXSHYDE Propargyl Alcohol Butine 2 diol 1,4 Butene 2 diol 1,4 . Butanediol 1,4 CHART 1 Butanediol 1,2 f Oxymethyl vinyl ketone f Butanone 2 diol 1.4 / Hexame t hylol-**• benzene Chloroallyl alcohol Propargyl aldehyde < 2,5 Dimethoxy 1,4 * dioxan — y butyrolactone (Plasticizers Esters (Alkyd resins (Textile waxes Tetrahydrofurane 3,4 oxide D ihydr of urane 4r" 3 Oxyt e t rahydrofuranc 1,3»4 Butanetriol(— Mellitic acid ) <_ Pyromellitic acid) See Chart 2 Polymers Acetal^— 34 7*/*.-3 Polyamide Resins —% Pyrrole Diazoamino compounds (insecticides) 7 R naphthyl pyroll- idine (antioxidant) 4 dichlorobutane —-*adipo- nitrile bexamethylene , diamine 1,6 Dodecahydrotriphergrlene Pyrollidine Butadiene 1,3 mixed polymers adipic acid; Butanediol 1,4-) Succinic 1 Acid CHART 1 (Continued) ACETYLENE + PORMAIDBHYDE Tetrahydro- furane Buna DicWjOrdibutyl ether Polyamines . 2,3 dichlorotetrahydro furane Polytetrahydrofurane phenantbrene £— *' 3 chloro 2 alkoxy- t e t rahydr ofurane Piperidene Penta methylene Piperidin Diamine 1#5 Alkyds Glutario Clutaric acid Polyamide ester dinitrile G-lutaric G-lutaric acid acid imide / , » NaGN Cyanbutvric f acid I Pentanediol 1,5 Polyamides Thiodibutyric acid Ssters for waxes, plasticizers resins / HaSH Dibutyric acid sulfone CHART 1 A V -Butvrolaot one Dipropyl ether Carboxylic acid Polyamide Alkyds Polyesters Plasticizers NaQH Chloro- butyric acid HG1 Esters 72.4--S amino butyric aoid Resins -HJ+IHj pyrollidone w Amino i ethyl pyrollidone N-vinyl Pyrollidone Polymers Textile assistants CHART 1 A (Continued) -oxy butyric amide V -Butyrolactone m3 Pyrrol Phe nosy- butyric acid Phenol Soligens Tetralon ▼ Phenyl butyric acid Benzene Phenylene dibutyric acid alkyds polyamids 3A7X.ft.-3 36 2 methyl tetrahydrofurane Pentine 3 did 2,3 Pentane did 2,3 I + 2H2 - HgO V piperylene ACETYLENE + ACETALDEHYDE CHART 2 Vinyl methyl ketone Butins - 3-ol-2 Butanol-2-on-3 p I + HgO -V 1 Acetaldehyde + 1 Acetylene — HoO Vinyl Acetylene *2 Butansdiol 2,3 Hexatriene 1,3»5 -2HoO 2,5 dimethyl tetrahydrofurane l,if dimethyl butadiene 1,5 (Hexadiene 2,4) ACETYLSHS + ACETALDEHYDE. Hexine - 3 - diol 2,5 Hexene- 3 - diol 2,5 • \ CHART 2 (Continued) + H2 -*y> -HgO Hexane diol 2,5 t *h2 2 Acetaldehyde + Acetylene -2^ Hexadione 2,3 (Acetonyl acetone) 3«